Conjugated dienamides, methods of production thereof, compositions containing same and uses thereof

ABSTRACT

Described are mixtures of at least four of the alkadienamides defined according to the structure:  
                 
 
wherein R represents C 1 -C 2  n-alkyl; R 1  is 2-methyl-1-propyl and R 2  is hydrogen, or R 1  and R 2  taken together is a moiety having the formula —(CH 2 ) n — wherein n is 4 or 5, or compositions containing substantial concentrations of such mixtures, prepared according to novel processes: (a) extraction of a ground substantially dried fruit of one of the  Piper  species,  Piper longum  Linn or  Piper peepuloides ; (b) natural product-forming synthesis; or (c) synthetic product-forming synthesis. Also described are uses of the thus-formed products for augmenting, enhancing or imparting an aroma, taste, chemesthetic effect and/or antibacterial effect in or to a consumable material and/or in the oral cavity and/or on the mammalian epidermis.

FIELD OF THE INVENTION

C₁₀-C₁₁-E2, E4-alkadienamide mixtures, obtainable synthetically or froma dried, ground Piper species, Piper longum Linn or Piper peepuloides,having beneficial flavor and sensory attributes in the oral cavity andon skin.

BACKGROUND OF THE INVENTION

The presence of C₁₀ and C₁₂ diene and triene amide derivatives in a widevariety of botanicals is known and the use thereof to impart flavorand/or a tingling and/or warming sensations in the oral cavity and onskin when used in foodstuffs, chewing gum, oral care products, hair careproducts, colognes, topical cosmetic products or medicinal products.Such C₁₀ and C₁₂ diene and triene amide derivatives are also disclosedas exhibiting biological activity, most notably anti-bacterial,anti-fungal and insecticidal activity. The most significant compoundswhich are members of the genus: “C₁₀ and C₁₂ diene and triene amidederivatives” are those disclosed as follows:

Spilanthol or affinin having the structure:

the use of which in oral care, skin care and medicinal products isdisclosed in Nakanatsu et al, Published European Patent Application EP1,121,927 A2.

Pellitorine, N-isobutyl-2,4-decadienamide having the structure:

lyeremide A (N-pyrrolidyl-2,4-decadienamide) having the structure:

lyeremide B (N-piperidyl-2,4-decadienamide) having the structure:

Piperine (N-piperidyl-5(3,4-methylenedioxyphenyl)-2,4-pentadienamide)and N-isobutyl-2,4-dodecadienamide are disclosed as constituents ofPiper guineense stem by Adesina et al. in “GC/MS Investigations of theminor constituents of Piper guineense stem”, Pharmazie 57 (2002)9, pages622-627. It is indicated in the introduction of the Adesina paper:“Piper guineense Schum and Thonn, Piperaceae . . . 1leaves and fruits .. . have been used as condiments, flavorants and generally as spices infoods. The sharp peppery taste of the fruit has contributed to itsacceptability and use in some food and drug preparations.”

Piperine, N-piperidyl-5(3,4-methylenedioxyphenyl)-2,4-pentadienamide, isalso disclosed in U.S. Pat. No. 6,365,601 as being extractable from thefruits of Piper species, including Piper longum, where it is present ina concentration of 4.5%. The corresponding 2,4-heptadienamide is alsoindicated to be extractable from Piper longum fruit by Das et al., “OneNew and Two Rare Alkamides from Two Samples of the Fruits of Piperlongum”, Natural Product Sciences, 4(l):23-25(1998).

However, nothing set forth in the prior art discloses mixtures of fouror more C₁₀-C₁₁-E2, E4-alkadienamide, particularly in highconcentration, e.g., between 3% and 100%, which mixtures are useful fortheir beneficial flavor and sensory attributes in the oral cavity and onskin. Furthermore, nothing in the prior art discloses such. C₁₀-C₁₁-E2,E4-alkadienamide mixtures as extractable from the ground, dried fruit ofthe Piper species, Piper longum Linn or Piper peepuloides.

SUMMARY OF THE INVENTION

The invention is directed to mixtures of at least fourC₁₀-C₁₁-E2,E4-alkadienamides, each of which alkadienamide is definedaccording to the structure:

wherein R represents C₁-C₂ n-alkyl; R₁ is 2-methyl-1-propyl and R₂ ishydrogen, or R₁ and R₂ taken together is a moiety having the formula—(CH₂)_(n)— wherein n is 4 or 5.

The mixtures of the invention are useful for augmenting, enhancing orimparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis. The term, ‘chemesthetic effect’ is herein intended tomean the sensations, tingling, warming and salivation in the oralcavity, including lips and tingling and warming on the human epidermis.Thus, the mixtures of the invention are useful in such materials asperfume compositions, perfumed articles, including cosmetics, soaps,detergents and fine fragrance compositions, foodstuffs, chewing gums,non-alcoholic beverages, alcoholic beverages, oral care products such asmouth washes, toothpastes, cough drops, cough syrups and throatlozenges, and skin care products including skin creams and lotions andhair care products including anti-dandruff compositions and shampoos.

The mixtures of the invention are hereinafter referred to as“C₁₀-C₁₁-E2,E4-alkadienamide mixtures”.

The C₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention may beobtained by means of (a) extraction of one of the Piper species, Piperlongum Linn or Piper peepuloides, (b) natural product-forming synthesisor (c) synthetic-product forming synthesis. The invention is thus alsodirected to such C₁₀-C₁₁-E2,E4-alkadienamide mixture-forming processes.

Furthermore, the invention is directed to a process for augmenting,enhancing or imparting an aroma, taste, chemesthetic effect and/orantibacterial effect in or to a consumable material and/or the oralcavity and/or the human epidermis comprising the step of admixing withsaid consumable material and/or introducing into the oral cavity and/orapplying to said human epidermis an aroma, taste, chemesthetic effectand/or antibacterial effect-effecting concentration and quantity of oneor more of such C₁₀-C₁₁-E2,E4-alkadienamide mixtures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic block flow diagram setting forth the processwhereby the C₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention areobtained by means of extraction of one of the Piper species, Piperlongum Linn or Piper peepuloides.

FIG. 2 is a portion of the GC-mass spectrum of the extract preparedaccording to the process whereby C₁₀-C₁₁-E2,E4-alkadienamide mixtures ofthe invention are obtained by means of extraction of the Piper species,Piper longum Linn.

FIG. 3 is a portion of the GC-mass spectrum of the extract preparedaccording to the process whereby C₁₀-C₁₁-E2,E4-alkadienamide mixtures ofthe invention are obtained by means of extraction of the Piper species,Piper peepuloides.

FIG. 4 is a set of comparitive bar graphs setting forth (a) rating forliking on a scale of 1-9; (b) rating for intensity on a scale of 1-9 and(c) duration in minutes for (i) extracts of Piper longum Linn and Piperpeepulides containing various concentrations ofC₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention, (ii)pellitorineand (iii) other sensate substances.

FIG. 5 is a set of bar graphs indicating duration in minutes for (i)extracts of Piper longum Linn and Piper peepulides containing variousconcentrations of C₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention,(ii) pellitorine and (iii) other sensate substances.

DETAILED DESCRIPTION OF THE INVENTION

The C₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention preferably areutilized in the practice of the invention in concentrations of fromabout 3% to about 100% by weight of the product in which the mixturesare employed. In addition, the C₁₀-C₁₁-E2,E4-alkadienamide mixtures ofthe invention preferably include the components:

-   -   i. N-isobutyl-E2, E4-decadienamide;    -   ii. N-isobutyl-E2, E4-undecadienamide;    -   iii. N-pyrollidyl-E2, E4-decadienamide; and    -   iv. N-piperidyl-E2, E4-decadienamide        having the structures:

When the C₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention areobtained by means of extraction of one of the Piper species, Piperlongum Linn or Piper peepuloides, the process employed comprises thesteps of:

-   -   i. milling dried fruits of at least one Piper species member        selected from the group consisting of Piper longum Linn and        Piper peepuloides in order to form a Piper longum Linn or Piper        peepuloides powder having an average particle size in the range        of from about 300 microns to about 800 microns;    -   ii. providing an extractor equipped with porous extractor        plates, preferably a percolator having screen-equipped baskets;    -   iii. placing portions of the milled Piper longum Linn or Piper        peepuloides powder on each of said porous extractor plates;    -   iv. intimately contacting the thus-supported milled Piper longum        Linn or Piper peepuloides powder with a first quantity of a        circulating given polar or non-polar solvent such as n-hexane at        a temperature in the range of from about 30° C. to about 50° C.        for a period of time of from about 10 hours to about 20 hours        with the solvent to solids weight ratio being from about 2.75:1        to about 3.25:1 thereby forming a first extract and        initially-extracted milled Piper longum Linn powder;    -   v. removing said first extract from the extractor;    -   vi. contacting the initially-extracted milled Piper longum Linn        or Piper peepuloides powder with a second quantity of a        circulating given polar or non-polar solvent, e.g., n-hexane at        a temperature in the range of from about 30° C. to about 50° C.        for a period of time of from about 10 hours to about 20 hours        with the solvent to solids weight ratio being from about 1.75:1        to about 2.25:1 thereby forming a second extract and        doubly-extracted milled Piper longum Linn or Piper peepuloides        powder;    -   vii. removing said second extract from the extractor;    -   viii. contacting the doubly-extracted milled Piper longum Linn        or Piper peepuloides powder with a third quantity of a        circulating given polar or non-polar solvent, e.g., n-hexane at        a temperature in the range of from about 30° C. to about 50° C.        for a period of time of from about 10 hours to about 20 hours        with the solvent to solids weight ratio being from about 0.75:1        to about 1.25:1 thereby forming a third extract and        triply-extracted milled Piper longum Linn or Piper peepuloides        powder;    -   ix. removing said third extract from the extractor;    -   x. combining said first extract, said second extract and said        third extract thereby forming a combined extract;    -   xi. subjecting the resulting combined extract to the unit        operation of evaporation thereby forming a concentrated extract;        and    -   xii. optionally fractionally distilling the resulting        concentrated extract at a vapor temperature in the range of from        about 55° C. to about 76° C., a liquid temperature in the range        of from about 109° C. to about 203° C. and a pressure of in the        range of from about 30 mm Hg to about 60 mm Hg thereby forming a        distillate.

Preferred variations of the above described process are as follows:

-   -   (a) the concentrated extract formed as a result of carrying out        step xi is extracted with 95% aqueous ethanol and the resulting        ethanol extract is subjected to the unit operation of        evaporation thereby forming a concentrated extract;    -   (b) the circulating extraction solvent is 95% aqueous ethanol        and the optional fractional distillation step, xii, is not        carried out; and.    -   (c) the circulating extraction solvent is 95% aqueous ethanol        and, immediately subsequent to carrying out the unit operation        of evaporation, step xi, the concentrated extract is extracted        with n-hexane thereby forming a fourth extract; the fourth        n-hexane extract is subjected to the unit operation of        evaporation thereby forming a concentrated extract and the        thus-concentrated extract is fractionally distilled at a vapor        temperature in the range of from about 55° C. to about 76° C., a        liquid temperature in the range of from about 109° C. to about        203° C. and a pressure of in the range of from about 30 mm Hg to        about 60 mm Hg thereby forming a distillate.

In addition, the above mentioned process may also comprise theadditional step of admixing the resulting extract, when the distillationstep is not employed, or distillate with a food-grade diluent.

When the C₁₀-C₁₁-E2,E4-alkadienamide mixture components of the inventionare obtained by means of natural product-forming synthesis, the processemployed comprises the steps of:

-   -   i. forming a natural amine selected from the group consisting of        isobutyl amine, piperidine and pyrrolidine;    -   ii. forming a natural amine acid salt thereof;    -   iii. optionally neutralizing the resulting amine salt to form        the corresponding amine;    -   iv. providing a natural E2,E4-dienal selected from the group        consisting of E2,E4-decadienal and E2,E4-undecadienal;    -   v. air oxidizing or microbiologically oxidizing the resulting        E2,E4-dienal thereby forming the corresponding E2,E4-dienoic        acid;    -   vi. esterifying the resulting E2,E4-dienoic acid with natural        alkanol or natural glycerol thereby forming the corresponding        E2,E4-dienoic acid ester;    -   vii. reacting the resulting E2,E4-dienoic acid ester with the        natural amine salt formed in step ii or the natural amine formed        in step iii in the presence of an ester-forming enzyme, such as        lipase; and    -   viii. recovering the resulting amide.

The resulting individual amides are then admixed with one anotherthereby forming the mixture of C₁₀-C₁₁-E2,E4-alkadienamide components ofthe invention.

In the above described process, when the amine initially formed isisobutyl amine, it is preferably produced by reacting natural valinewith a natural aromatic ketone or aromatic aldehyde to form an iminecarboxylic acid; isomerizing and decarboxylating the resulting iminecarboxylic acid to form a decarboxylated imine; hydrolyzing theresulting decarboxylated imine at a pH of from about 1.5 to about 3.5threreby forming the natural isobutyl amine salt.

Preferably, the esterification in step vi., above of the E2,E4-dienoicacid is carried out with natural ethanol.

Thus, for example, in accordance with the above described genericprocess, the specific process for the production of naturalN-isobutyl-E2, E4-decadienamide having the structure:

comprising the steps of:

-   -   i. forming natural isobutyl amine acid salt by (a) reacting        natural valine with natural anisaldehyde to form an imine; (b)        isomerizing the imine and effecting decarboxylation thereof        thereby forming a decarboxylated imine; and (c) effecting acid        hydrolysis of the decarboxylated imine thereby forming the acid        salt of isobutyl amine; and (d) optionally neutralizing the acid        salt of isobutyl amine to form isobutyl amine;    -   ii. forming natural ethyl 2E,4E-decadienoate by (a) thermal        isomerization of natural ethyl 2Z,4E-decadienoate; (b)air        oxidation of natural 2E,4E-decadienal in admixture with ethanol;        or (c) microbiological oxidation of natural 2E, 4E-decadienal;.    -   iii. reacting the resulting ethyl 2E,4E-decadienoate with the        natural isobutyl amine or salt thereof in the presence of an        esterification enzyme with the mole ratio of decadienoate:amine        or salt thereof being from 1:1 to about 3:1 at a temperature of        from about 30° C. to about 80° C. for a period of time of from        about 20 to about 100 hours according to the reaction:        and    -   iv. recovering the resulting natural N-isobutyl-E2,        E4-decadienamide.

When the C₁₀-C₁₁-E2,E4-alkadienamide mixture components of the inventionare obtained by means of synthetic product-forming synthesis, theprocess employed comprises the steps of dissolving an E2, E4-dienoicacid selected from the group consisting of E2, E4-decadienoic acid andE2,E4-undecadienoic acid in a compatible solvent thereby forming aE2,E4-dienoic acid solution; admixing the resulting E2,E4-dienoic acidsolution with from about 1 to about 2 equivalents of an acid-activatingreagent selected from the group consisting of a lower alkyl haloformate,an N,N′-dialiphatic or cycloaliphatic azodicarbodiimide and adihalo-oxalate at a temperature in the range of from about 0° C. toabout 20° C. thereby forming an intermediate; cooling the resultingintermediate-containing solution to a temperature in the range of fromabout −10° C. to about +10° C. and, when using as a reactant the loweralkyl haloformate or the dihalooxalate, admixing therewith atri-loweralkyl amine while maintaining the temperature of the mixturebelow +10° C.; then aging the resulting intermediate-containing productat ambient conditions for a period of from about 0.5 to about 3 hours,according to the reaction:

filtering the resulting product; separating the resulting filtrate andcooling the resulting filtrate to a temperature in the range of fromabout −5° C. to +5° C.; admixing the resulting cooled filtrate with fromabout 1 to about 4 equivalents of an amine selected from the groupconsisting of isobutyl amine, piperidine and pyrrolidine at ambientconditions thereby effecting an amidation reaction, and thereby formingan amide defined according to the structure:

and recovering the resulting amide.

The resulting individual amides are then admixed with one anotherthereby forming the mixture of C₁₀-C₁₁-E2,E4-alkadienamide components ofthe invention.

When using as an acid activating agent ethyl chloroformate, the reactionproceeds as follows:

The thus-formed mixtures of C₁₀-C₁₁-E2,E4-alkadienamide components ofthe invention may each be admixed with a substantial quantity andconcentration of a tingling sensate, for example, one or more of suchsensates selected from the group consisting of substantially purespilanthol having the structure:

Acmella ciliata, Acmella (Spilanthes) oppositifolia, Anacyclus pyrethrumD.C., Spilanthes acmella L. var. oleraceae (Jambu) and Heliopsislongipes S. F. Blake (Chilcuan) and the resulting mixtures may then beused for augmenting, enhancing or imparting an aroma, taste,chemesthetic effect and/or antibacterial effect in or to a consumablematerial and/or the oral cavity and/or the human epidermis by means of aprocess comprising the step of admixing with said consumable materialand/or introducing into the oral cavity and/or applying to said humanepidermis an aroma, taste, chemesthetic effect and/or antibacterialeffect-effecting concentration and quantity of the resulting mixture.

The following Table I sets forth examples of processes and compositionswhere the mixtures of C₁₀-C₁₁-E2,E4-alkadienamide components of theinvention are utilized. Each of the useful ingredients set forth in thecited U.S. patent and patent application references, including theexamples thereof is usable in the practice of the invention, and herebyincorporated by reference. TABLE I Nature of Use of the ReferenceContaining Examples mixtures of C₁₀-C₁₁-E2,E4- Where the mixtures ofalkadienamide components C₁₀-C₁₁-E2,E4-alkadienamide of the Inventioncomponents of the Invention are Utilizable Skin care U.S. Pat. No.6,096,324 Skin care moisturizers and U.S. Pat. No. 6,099,849 cleanersCosmetic compositions U.S. Pat. No. 6,190,679 Oral sensates, flavorApplication for U.S. Pat. No. 2002/ enhancers and potentiators 0122778A1 published on Sep. 5, 2002 Aroma compositions for Application for U.S.Pat. No. 2003/ foodstuffs and oral hygiene 0096731 A1 published on May22, 2003 Use of ferulic acid amides Application for U.S. Pat. No. 2003/as flavor compounds 0152682 A1 published on Aug. 14, 2003 Food,pharmaceutical European Published Application EP and personal careproducts 1,121,927 A2 published Aug. 8, 2001 Anti-dandruff andApplication for U.S. patent Ser. No. anti-itch compositions 10/067,596filed on Feb. 5, 2002 Taste and sensory Application for U.S. patent Ser.No. effect compositions 10/411,672 filed on Apr. 11, 2003

As used herein olfactory effective amount is understood to mean theamount of compound in flavor compositions, oral care compositions, nasalcare compositions, skin care compositions, hair and scalp carecompositions, cosmetic compositions and other consumable materials asdefined supra, the individual component will contribute to itsparticular olfactory characteristics, but the flavor, taste and aromaeffect on the overall composition will be the sum of the effects of eachof the flavor ingredients. As used herein taste effects includebitterness and tingling effects. Thus the compounds of the invention canbe used to alter the taste characteristics of the flavor composition bymodifying the taste reaction contributed by another ingredient in thecomposition. The amount will vary depending on many factors includingother ingredients, their relative amounts and the effect that isdesired.

The level of use of the mixtures of C₁₀-C₁₁-E2,E4-alkadienamidecomponents of the invention in products is greater than 10 parts perbillion, generally provided at a level of from about 50 parts perbillion to about 200 parts per million in the finished product, morepreferably from about 100 parts per billion to about 100 parts permillion by weight.

The usage level of the mixtures of C₁₀-C₁₁-E2,E4-alkadienamidecomponents of the invention varies depending on the product in which themixtures of C₁₀-C₁₁-E2,E4-alkadienamide components of the invention areemployed. For example, alcoholic beverages the usage level is from about0.5 to about 25 parts per million, preferably from about 2 to about 10and most preferably from about 5 to about 10 parts per million byweight. Non-alcoholic beverages are flavored at levels of from about 25parts per billion to about 2 parts per million, preferably from about100 parts per billion to about 0.5 parts per million and in highlypreferred situations of from about 150 to about 400 parts per billion.Snack foods can be advantageously flavored using the mixtures ofC₁₀-C₁₁-E2,E4-alkadienamide components of the invention at levels offrom about 5 to about 250 parts per million, preferably from about 25 toabout 200 and most preferably from about 35 to about 75 parts permillion by weight.

The term “foodstuff” as used herein includes both solid and liquidingestible materials for man or animals, which materials usually do, butneed not, have nutritional value. Thus, foodstuffs include meats,gravies, soups, convenience foods, malt, alcoholic and other beverages,milk and dairy products, seafood, including fish, crustaceans, mollusksand the like, candies, vegetables, cereals, soft drinks, snacks, dog andcat foods, other veterinary products and the like.

When the mixtures of C₁₀-C₁₁-E2,E4-alkadienamide components of theinvention are used in a flavoring composition, they can be combined withconventional flavoring materials or adjuvants. Such co-ingredients orflavor adjuvants are well known in the art for such use and have beenextensively described in the literature. Requirements of such adjuvantmaterials are: (1) that they be non-reactive with the components of themixtures of C₁₀-C₁₁-E2,E4-alkadienamides of the invention (2) that theybe organoleptically compatible with the components of the mixtures ofC₁₀-C₁₁-E2,E4-alkadienamides of the invention whereby the flavor of theultimate consumable material to which the components of the mixtures ofC₁₀-C₁₁-E2,E4-alkadienamides of the invention are added is notdetrimentally affected by the use of the adjuvant; and (3) that they beingestible acceptable and thus nontoxic or otherwise non-deleterious.Apart from these requirements, conventional materials can be used andbroadly include other flavor materials, vehicles, stabilizers,thickeners, surface active agents, conditioners and flavor intensifiers.

Such conventional flavoring materials include saturated fatty acids,unsaturated fatty acids and amino acids; alcohols including primary andsecondary alcohols, esters, carbonyl compounds including ketones,lactones; other cyclic organic materials including benzene derivatives,acyclic compounds, heterocyclics such as furans, pyridines, pyrazinesand the like; sulfur-containing compounds including thiols, sulfides,disulfides and the like; proteins; lipids, carbohydrates; so-calledflavor potentiators such as monosodium glutamate; magnesium glutamate,calcium glutamate, guanylates and inosinates; natural flavoringmaterials such as hydrolyzates, cocoa, vanilla and caramel; essentialoils and extracts such as anise oil, clove oil and the like andartificial flavoring materials such as vanillyl butyl ether, ethylvanillin and the like.

Specific preferred flavor adjuvants include but are not limited to thefollowing: anise oil; ethyl-2-methyl butyrate; vanillin; cis-3-heptenol;cis-3-hexenol; trans-2-heptenal; butyl valerate; 2,3-diethyl pyrazine;methyl cyclo-pentenolone; benzaldehyde; valerian oil;3,4-dimeth-oxphenol; amyl acetate; amyl cinnamate; γ-butyryl lactone;furfural; trimethyl pyrazine; phenyl acetic acid; isovaleraldehyde;ethyl maltol; ethyl vanillin; ethyl valerate; ethyl butyrate; cocoaextract; coffee extract; peppermint oil; spearmint oil; clove oil;anethol; cardamom oil; wintergreen oil; cinnamic aldehyde;ethyl-2-methyl valerate; γ-hexenyl lactone; 2,4-decadienal;2,4-heptadienal; methyl thiazole alcohol (4-methyl-5-β-hydroxyethylthiazole); 2-methyl butanethiol; 4-mercapto-2-butanone;3-mercapto-2-pentanone; 1-mercapto-2-propane; benzaldehyde; furfural;furfuryl alcohol; 2-mercapto propionic acid; alkyl pyrazine; methylpyrazine; 2-ethyl-3-methyl pyrazine; tetramethyl pyrazine; polysulfides;dipropyl disulfide; methyl benzyl disulfide; alkyl thiophene;2,3-dimethyl thiophene; 5-methyl furfural; acetyl furan; 2,4-decadienal;guaiacol; phenyl acetaldehyde; β-decalactone; d-limonene; acetoin; amylacetate; maltol; ethyl butyrate; levulinic acid; piperonal; ethylacetate; n-octanal; n-pentanal; n-hexanal; diacetyl; monosodiumglutamate; monopotassium glutamate; sulfur-containing amino acids, e.g.,cysteine; hydrolyzed vegetable protein; 2-methylfuran-3-thiol;2-methyldihydrofuran-3-thiol; 2,5-dimethylfuran-3-thiol; hydrolyzed fishprotein; tetramethyl pyrazine; propylpropenyl disulfide; propylpropenyltrisulfide; diallyl disulfide; diallyl trisulfide; dipropenyl disulfide;dipropenyl trisulfide; 4-methyl-2-[(methylthio)-ethyl]-1,3-dithiolane;4,5-dimethyl-2-(methylthiomethyl)-1,3-dithiolane; and4-methyl-2-(methylthiomethyl)-1,3-dithiolane.

The components of the mixtures of C₁₀-C₁₁-E2,E4-alkadienamides of theinvention or compositions incorporating them, as mentioned above, can becombined with one or more vehicles or carriers for adding them to theparticular product. Vehicles can be water-soluble or oil-soluble edibleor otherwise suitable materials such as triacetin, vegetable oil,triethyl citrate, ethyl alcohol, propylene glycol, water and the like.Carriers include materials such as gum arabic, carrageenan, xanthan gum,guar gum and the like.

Components of the mixtures of C₁₀-C₁₁-E2,E4-alkadienamides of theinvention prepared according to the invention can be incorporated withthe carriers by conventional means such as spray-drying, extrusion,drum-drying and the like. Such carriers can also include materials forcoacervating the components of the mixtures ofC₁₀-C₁₁-E2,E4-alkadienamides of the invention to provide encapsulatedproducts, as set forth supra. When the carrier is an emulsion, theflavoring composition can also contain emulsifiers such as mono- anddiglycerides or fatty acids and the like. With these carriers orvehicles, the desired physical form of the compositions can be prepared.

The quantity of the components of the mixtures ofC₁₀-C₁₁-E2,E4-alkadienamides of the invention utilized should besufficient to impart the desired flavor characteristic to the product,but on the other hand, the use of an excessive amount of the componentsof the mixtures of C₁₀-C₁₁-E2,E4-alkadienamides of the invention is notonly wasteful and uneconomical, but in some instances, too large aquantity may unbalance the flavor or other organoleptic properties ofthe product consumed. The quantity used will vary depending upon theultimate foodstuff; the amount and type of flavor initially present inthe foodstuff; the further process or treatment steps to which thefoodstuff will be subjected; regional and other preference factors; thetype of storage, if any, to which the product will be subjected; and thepreconsumption treatment such as baking, frying and so on, given to theproduct by the ultimate consumer. Accordingly, the terminology“effective amount” and “sufficient amount” is understood in the contextof the present invention to be quantitatively adequate to alter theflavor of the foodstuff.

Referring to FIG. 1, dried Piper longum Linn or Piper peepuloides fruitat location 10 is transported via conveyor 11 into milling apparatus 12wherein it is milled to a particle size in the range of from about 300microns to about 800 microns. The milled particles are conveyed via line13 into extractor 14 onto supported screens 15 (acting as extractioncolumn stages). The temperature profiles and rates of heat transfer inextractor (percolator) 14 are controlled by means of fluid pumped intoheating jacket 22 entering at inlet 24 and exiting at outlet 23.Extraction solvent (e.g., n-hexane) flows from solvent supply vessel 16past control valve 18 through line 17 into extractor (percolator) 14,with the extraction solvent being recirculated through the supportedscreens and through line 19 past valve 20 using circulating solvent pump21. After a period of time in the range of 10-20 hours, with thesolvent:solids ratio being from about 2.75:1 to 3.25:1 the operation ofthe pump 21 is temporarily discontinued while the liquid extractcontaining extracted product is removed from the extractor via line 25past control valve 26 into extract holding tank 90. Then, for a secondtime, extraction solvent, such as n-hexane, flows from solvent supplyvessel 16 past control valve 18 through line 17 into extractor(percolator) 14, with the extraction solvent being recirculated throughthe supported screens and through line 19 past valve 20 usingcirculating solvent pump 21. After a period of time in the range of10-20 hours, with the solvent:solids ratio being from about 1.75:1 to2.25:1 the operation of the pump 21 is temporarily discontinued whilethe liquid extract containing extracted product is removed from theextractor via line 25 past control valve 26 into extract holding tank90. Then, for a third time, extraction solvent, such as n-hexane, flowsfrom solvent supply vessel 16 past control valve 18 through line 17 intoextractor, also known as percolator, 14, with the extraction solventbeing recirculated through the supported screens and through line 19past valve 20 using circulating solvent pump 21. After a period of timein the range of 10-20 hours, with the solvent:solids ratio being fromabout 0.75:1 to 1.25:1 the operation of the pump 21 is discontinuedwhile the liquid extract containing extracted product is removed fromthe extractor via line 25 past control valve 26 into extract holdingtank 90. The combined extracts in holding vessel 90 is then passedthrough line 27 past control valve 28 into filtration apparatus 29 whereprecipitate is discarded via conveyor 30 to disposal means 31 andfiltrate passes through line 32 past control valve 33 into evaporator34. On operation of evaporator 34, overhead solvent vapor is recycledvia line 35 past control valve 36 back to solvent supply vessel 16.Concentrated extract is passed through line 37 past control valve 38into storage vessel 40. In the alternative, concentrated extract ispassed through line 41 past control valve 42 into fractionaldistillation column 43 where residue is removed through line 44 andpassed into disposal means 45 and overhead distillate (containingC₁₀-C₁₁-E2,E4-alkadienamide mixtures of the invention) is passed throughline 46 and heat exchanger 47 past control valve 48 into product vessel53 through line 49 past control valve 50, and into ‘discarded fraction’vessel 54 through line 51 past control valve 52. In the alternative,when the circulating extraction solvent through extractor 14 is ethanol,concentrated extract is passed through line 55 past control valve 56into liquid-liquid multistage extraction column 57 (equipped forn-hexane:ethanol exchange) while simultaneously passing n-hexane fromstorage vessel 58 through line 59 past control valve 60 into multi-stageextractor 57 countercurrent to the flow of the concentrated extractentering the multistage extractor 57 from line 34. Ethanol fractionexits from extractor 57 via line 71 into ethanol fraction storage vessel72. n-Hexane extract exiting the extractor 57 through line 61 pastcontrol valve 62 is concentrated in evaporator 63. Hexane solventexiting evaporator 63 passes through line 67 past valve 66 into vessel68 from which the solvent is recycled via line 69 past control valve 70into an alternative solvent supply vessel (which is separate from asolvent supply vessel that would be the source of ethanol supply) 16.Simultaneously, concentrated hexane extract exits from evaporator 63 vialine 64 past control valve 65 into distillation column 43 where residueis removed through line 44 and passed into disposal means 45 andoverhead distillate, containing C₁₀-C11-E2,E4-alkadienamide mixtures ofthe invention, is passed through line 46 and heat exchanger 47 pastcontrol valve 48 into product vessel 53 through line 49 past controlvalve 50; and into discarded fraction vessel 54 through line 51 pastcontrol valve 52.

Referring to FIG. 2, the “X” axis, horizontal axis, is indicated byreference numeral 211 and the “Y” axis is indicated by reference numeral210. The peak indicated by reference numeral 200 is forN-isobutyl-E2,E4-decadienamide. The peak indicated by reference numeral201 is for N-isobutyl-E2,E4-undecadienamide. The peak indicated byreference numeral 202 is for N-pyrrolidyl-E2,E4-decadienamide. The peakindicated by reference numeral 203 is forN-piperidyl-E2,E4-decadienamide.

Referring to FIG. 3, the “X’ axis, horizontal axi, is indicated byreference numeral 311 and the “Y” axis is indicated by reference numeral310. The peak indicated by reference numeral 300 is forN-isobutyl-E2,E4-decadienamide. The peak indicated by reference numeral301 is for N-isobutyl-E2,E4-undecadienamide. The peak indicated byreference numeral 302 is for N-pyrrolidyl-E2,E4-decadienamide. The peakindicated by reference numeral 303 is forN-piperidyl-E2,E4-decadienamide.

Referring to FIG. 4, the “Y” axis, indicated by reference numeral 400indicates (a) the scale of 1-9 for measuring liking and intensity and(b) duration in minutes. The “X” axis, the horizontal axis, is indicatedby reference numeral 410. The bar graphs indicated with the suffix “a”are for intensity. The bar graphs indicated by the suffix “b” are forliking. The bar graphs indicated by the suffix “c” are for duration.

The following Table II sets forth the specific substance being comparedidentified by a specific reference numeral: TABLE II Reference Substancebeing compared Numeral Jambu Extract 30% (tested at 10 ppm) 411 NaturalSpilanthol 95% (tested at 10 ppm) 412 Chilcuan Extract 25% (tested at 10ppm) 413 Piper peepuloides (contains 5% mixture of C₁₀-C₁₁-E2,E4- 414alkadienamides of the invention) (tested at 10 ppm) Piper longum Linn(contains 35% mixture of C₁₀-C₁₁-E2,E4- 415 alkadienamides of theinvention)(tested at 10 ppm) Pelloritine 98% (tested at 10 ppm) 416N-isobutyl-E2,Z6-dodecadienamide (tested at 10 ppm) 417N-isobutyl-E2,E4,Z8-undecatrienamide (tested at 10 ppm) 418

Referring to FIG. 5, the “Y” axis indicated by reference numeral 500indicates the time duration in minutes. The “X” axis, the horizontalaxis, is indicated by reference numeral 510.

The following Table III sets forth the specific substance being comparedidentified by a specific reference numeral: TABLE III ReferenceSubstance being compared Numeral Jambu Extract 30% (tested at 10 ppm)511 Chilcuan Extract 25% (tested at 10 ppm) 512 Chilcuan Extract 25%(tested at 20 ppm) 513 Piper longum Linn (contains 35% mixture ofC₁₀-C₁₁-E2,E4- 514 alkadienamides of the invention)(tested at 10 ppm)Piper longum Linn (contains 25% mixture of C₁₀-C₁₁-E2,E4- 515alkadienamides of the invention)(tested at 10 ppm) Piper longum Linn(contains 7% mixture of C₁₀-C₁₁-E2,E4- 516 alkadienamides of theinvention)(tested at 10 ppm) Piper peepuloides (contains 5% mixture ofC₁₀-C₁₁-E2,E4- 517 alkadienamides of the invention) (tested at 10 ppm)Pelloritine 98% (tested at 10 ppm) 518 Natural spilanthol 95% (tested at20 ppm) 519 Natural spilanthol 95% (tested at 10 ppm) 520N-isobutyl-E2,E4,Z8-undecatrienamide (tested at 20 ppm) 521N-isobutyl-E2,E4,Z8-undecatrienamide (tested at 10 ppm) 522N-isobutyl-E2,Z6-nonadienamide (tested at 10 ppm) 523N-isobutyl-E2,Z6-undecadienamide (tested at 10 ppm) 524

The following examples are provided as specific embodiments of thepresent invention. Other modifications of this invention will be readilyapparent to those skilled in the art, without departing from the scopeof this invention. As used herein, both the specification and thefollowing examples all percentages are weight percent unless noted tothe contrary.

EXAMPLE 1 Preparation of Components of Mixtures ofC₁₀-C₁₁-E2,E4-Alkadienamides

The following reaction sequence was used to prepare the specificcompounds described by the NMR data set forth below:

2,4-Dienoic acid was dissolved in dichloromethane to whichethylchloroformate was added in 1.0 to 2.0 equivalents at temperatureranging from 0° C. to room temperature, most preferably from 10° C. to20° C. The resulting solution was cooled to −10° C. to +10° C., andtriethylamine was added in 1.0 to 2.0 equivalents such that thetemperature range is below 10° C. and the mixture aged for 1 hour atroom temperature. The mixture was filtered, and the filtrate cooled to0° C.

The amine was added in 1.0 to 4.0 equivalents and the reaction was agedfor about 1-3 hours at room temperature. The reaction was quenched with10% aqueous hydrochloric acid, washed with 10% sodium hydroxide followedby sodium chloride solution, and the solvent was removed.

The crude product was purified by distillation or recrystallizationdepending on the physical properties. The reaction occurred in 40-60%mole yields based on the acids.

The amides were synthesized according to the general scheme above withthe following specific examples. Equivalents set out are moleequivalents based on starting acid, yields are purified chemical yieldsbased on starting acid.

N-isobutyl E2,E4-decadienamide E2,E4-decadienoic acid 1 eq, ethylchloroformate 1.5 eq, triethylamine 1.5 eq, isobutylamine 3.0 eq, quenchas per general procedure, yield=45%.

0.89 ppm (t, 3H, J=6.92Hz) 0.92 ppm (d, 6H, J=6.71Hz) 1.30 ppm (m, 4H)1.42 ppm (pentet, 2H, J=7.19Hz) 1.80 ppm (septet, 1H, J=6.73Hz) 2.14 ppm(q, 2H, J=6.88Hz) 3.16 ppm (t, 2H, J=6.48Hz) 5.57 ppm (br. s, 1H) 5.76ppm (d, 1H, J=15.04Hz) 6.04-6.17 ppm (m, 2H) 7.19 ppm (d, 1H, J=14.98Hz,of d, J=9.85Hz)

N-isobutyl E2,E4-undecadienamide E2,E4-undecadienoic acid 1 eq, ethylchloroformate 1.5 eq, triethylamine 1.5 eq, isobutylamine 3.0 eq, quenchas per general procedure, yield=40%.

0.88 ppm (t, 3H, J=6.82Hz) 0.92 ppm (d, 6H, J=6.70Hz) 1.28 ppm (m, 6H)1.41 ppm (pentet, 2H, J=6.88Hz) 1.80 ppm (septet, 1H, J=6.73Hz) 2.14 ppm(q, 2H, J=6.83Hz) 3.16 ppm (t, 2H, J=6.48Hz) 5.55 ppm (br. s, 1H) 5.76ppm (d, 1H, J=15.03Hz) 6.02-6.17 ppm (m, 2H) 7.19 ppm (d, 1H, J=14.98Hz,of d, J=9.86Hz)

N-piperidyl E2,E4-decadienamide E2,E4-decadienoic acid 1 eq, ethylchloroformate 1.1 eq, triethylamine 1.2 eq, piperidine 1.25 eq, quenchas per general procedure, yield=40%.

0.89 ppm (t, 3H, J=6.92Hz) 1.30 ppm (m, 4H) 1.42 ppm (pentet, 2H,J=7.19Hz) 1.56 ppm (m, 4H) 1.64 ppm (m, 2H) 2.14 ppm (q, 2H, J=7.04Hz)3.49 ppm (br. s, 2H) 3.60 ppm (br. s, 2H) 6.06 ppm (m, 1H) 6.18 ppm (2d,1H, J=10.82Hz) 6.27 ppm (d, 1H, J=14.79Hz) 7.23 ppm (d, 1H, J=14.74Hz,of d, J=10.73Hz)

N-pyrrolidyl E2,E4-decadienamide E2,E4-decadienoic acid 1 eq, ethylchloroformate 1.1 eq, triethylamine 1.2 eq, pyrrolidine 1.5 eq, quenchas per general procedure, yield=58%.

0.89 ppm (t, 3H, J=6.90Hz) 1.30 ppm (m, 4H) 1.42 ppm (pentet, 2H,J=7.10Hz) 1.86 ppm (pentet, 2H, J=7.40Hz) 1.96 ppm (pentet, 2H,J=6.50Hz) 2.15 ppm (q, 2H, J=7.10Hz) 3.53 ppm (2t, 4H, J=6.96Hz)6.06-6.18 ppm (m, 2H) 6.09 ppm (d, 1H, J=14.87Hz) 7.27 ppm (d, 1H,J=14.83Hz, of d, J=10.57Hz)

EXAMPLE IIA Preparation of Fragrance for Use in Shampoo of Example IIB

The following fragrance was prepared for use with the shampoo of ExampleII: Ingredients Parts by Weight α-irone 7.0 myristicin 4.02-methoxynaphthalene 3.0 benzaldehyde 2.0 β-phenylethyl alcohol 12.0nerol 7.0 eugenol 8.0 isoeugenol 2.0 amyl salicylate 4.0 β-caryophyllene14.0 cedryl acetate 16.0 cyclohexyl salicylate 4.0 γ-dodecalactone 3.0geranyl anthranilate 3.0

EXAMPLE IIB Preparation of Fragrance-Containing Shampoo Base for Use inConjunction with Examples IIC, infra

At the rate of 0.8%, the fragrance was prepared according to Example IIAand admixed with the following aqueous shampoo base: Component Parts byWeight ammonium lauryl sulfate (27% 56.0 aqueous solution) citric acid0.50 sodium citrate 0.50 coconut monoethanolamide 5.0 ethylene glycoldistearate 3.0 methyl paraben 0.50 propyl paraben 0.50 color solution0.20 water 33.8

EXAMPLE IIC

To the shampoo of Example IIB, zinc pyrithione was added at the rate of1%, and the following mixture, the components of which were preparedaccording to Example I, were added at the rate of 0.3%: IngredientsParts by Weight N-isobutyl-E2,E4- 45 decadienamide N-isobutyl-E2,E4- 25undecadienamide N-pyrollidyl-E2,E4- 5 decadienamide N-piperidyl-E2,E4-10 decadienamide

A substantial tingling effect was exerted during use and 5 minutes postuse of the shampoo, having a value of 9 on a scale of 1-9.

EXAMPLE III EXAMPLE IIIA Punch Flavor

The following punch flavor was prepared: Ingredients Parts by Weight(grams) benzaldehyde 500 single fold orange oil 415 single foldgrapefruit flavor 33.4 ethyl caproate 16.6 ethyl butyrate 16.6 ethylisovalerate 8.3 ethyl propionate 3.3 alpha ionone 0.1 jasmin absolute0.1 geraniol 3.3 isoamyl acetate 3.3 4,8-dimethyl-3,7-nonadien-2-yl 6.52-methyl-2-pentenoate

EXAMPLE IIIB

(i) Powder Flavor

20 Grams of the flavor composition of Example IIIA was emulsified in asolution containing 300 grams of gum acacia and 700 grams of water. Theemulsion was spray-dried with a Bowen Lab Model Drier utilizing 250cubic feet per minuite of air with an inlet temperature of 500° F. andan outlet temperature of 200° F. and a wheel speed of 50,000 r,p,m.

(ii) Paste Blend

A mixture of 300 grams of the liquid flavor of Example IIIA and 1 kg. ofCab-O-Sil M-5 (Cabot Corporation of Boston, Mass.) silica was preparedby dispersing the silica in the liquid flavor with vigorous stirring.The powder flavor prepared according to part (i) was then blended intothe resulting viscous liquid with stirring at 25° C. for a period ofabout 30 minutes resulting in a sustained release flavor paste.

EXAMPLE IIIC

Into a Hobart mixer, 98.15 parts by weight of sorbitol was admixed with0.05 parts by weight of FD&C yellow #6 lake (Warner Jenkinson).

To the resulting mixture, with stirring the following substances wereadded:

-   -   (a) 0.60 parts by weight of the paste blend of Example IIIB;    -   (b) 0.40 parts by weight of groundcitric acid; and

(c) 0.30 parts by weight of the following mixture, the components ofwhich were prepared according to Example I: Ingredients Parts by Weight(grams) N-Isobutyl-E2,E4-undecadienamide 45N-isobutyl-E2,E4-undecadienamide 25 N-pyrollidyl-E2,E4-decadienamide 5N-piperidyl-E2,E4-decadienamide 10

0.8 parts by weight of magnesium stearate was then added to theresulting mixture and the resulting mixture was tabletted, providingorange-punch-flavored tablets with a pleasant ‘tingle’ effect.

1. A mixture of at least four alkadienamides, each of which is definedaccording to the structure:

wherein R represents C₁-C₂ n-alkyl; R₁ is 2-methyl-1-propyl and R₂ ishydrogen, or R₁ and R₂ taken together is a moiety having the formula—(CH₂)_(n)— wherein n is 4 or
 5. 2. A composition of matter comprisingfrom about 3% by weight up to about 100% by weight of the composition ofclaim
 1. 3. The mixture of claim 1 comprising the compounds: i.N-isobutyl-E2, E4-decadienamide; ii. N-isobutyl-E2, E4-undecadienamide;iii. N-pyrollidyl-E2, E4-decadienamide; and iv. N-piperidyl-E2,E4-decadienamide
 4. The mixture of claim 2 comprising the compounds: i.N-isobutyl-E2, E4-decadienamide; ii. N-isobutyl-E2, E4-undecadienamide;iii. N-pyrollidyl-E2, E4-decadienamide; and iv. N-piperidyl-E2,E4-decadienamide
 5. A process for forming a composition having asubstantial concentration of the mixture of claim 1 comprising the stepsof: i. milling dried fruits of at least one Piper species memberselected from the group consisting of Piper longum Linn and Piperpeepuloides in order to form a Piper longum Linn or Piper peepuloidespowder having an average particle size in the range of from about 300microns to about 800 microns; ii. providing an extractor equipped withporous extractor plates; iii. placing portions of the milled Piperlongum Linn or Piper peepuloides powder on each of said porous extractorplates; iv. contacting the thus-supported milled Piper longum Linn orPiper peepuloides powder with a first quantity of a circulating givenpolar or non-polar solvent at a temperature in the range of from about30° C. to about 50° C. for a period of time of from about 10 hours toabout 20 hours with the solvent to solids weight ratio being from about2.75:1 to about 3.25:1 thereby forming a first extract andinitially-extracted milled Piper longum Linn powder; v. removing saidfirst extract from the extractor; vi. contacting the initially-extractedmilled Piper longum Linn or Piper peepuloides powder with a secondquantity of a circulating given polar or non-polar solvent at atemperature in the range of from about 30° C. to about 50° C. for aperiod of time of from about 10 hours to about 20 hours with the solventto solids weight ratio being from about 1.75:1 to about 2.25:1 therebyforming a second extract and doubly-extracted milled Piper longum Linnor Piper peepuloides powder; vii. removing said second extract from theextractor; viii. contacting the doubly-extracted milled Piper longumLinn or Piper peepuloides powder with a third quantity of a circulatinggiven polar or non-polar solvent at a temperature in the range of fromabout 30° C. to about 50° C. for a period of time of from about 10 hoursto about 20 hours with the solvent to solids weight ratio being fromabout 0.75:1 to about 1.25:1 thereby forming a third extract andtriply-extracted milled Piper longum Linn or Piper peepuloides powder;ix. removing said third extract from the extractor; x. combining saidfirst extract, said second extract and said third extract therebyforming a combined extract; xi. subjecting the resulting combinedextract to the unit operation of evaporation thereby forming aconcentrated extract; and xii. optionally fractionally distilling theresulting concentrated extract at a vapor temperature in the range offrom about 55° C. to about 76° C., a liquid temperature in the range offrom about 109° C. to about 203° C. and a pressure of in the range offrom about 30 mm Hg to about 60 mm Hg thereby forming a distillate. 6.The process of claim 5 wherein the extractor is a percolator and theporous plates are screen baskets.
 7. The process of claim 5 wherein thecirculating extraction solvent is n-hexane.
 8. The process of claim 5wherein the resulting concentrated extract formed according to step (xi)is fractionally distilled at a vapor temperature in the range of fromabout 55° C. to about 76° C., a liquid temperature in the range of fromabout 109° C. to about 203° C. and a pressure of in the range of fromabout 30 mm Hg up to about 60 mm Hg thereby forming a distillate.
 9. Theprocess of claim 8 wherein the concentrated extract formed as a resultof carrying out step (xi) is extracted with 95% aqueous ethanol and theresulting ethanol extract is subjected to the unit operation ofevaporation thereby forming a concentrated extract.
 10. The process ofclaim 5 wherein the circulating extraction solvent is 95% aqueousethanol.
 11. The process of claim 5 wherein the circulating extractionsolvent is 95% aqueous ethanol and, immediately subsequent to carryingout the unit operation of evaporation, step xi, the concentrated extractis extracted with n-hexane thereby forming a fourth extract; the fourthn-hexane extract is subjected to the unit operation of evaporationthereby forming a concentrated extract and the thus-concentrated extractis fractionally distilled at a vapor temperature in the range of fromabout 55° C. to about 76° C., a liquid temperature in the range of fromabout 109° C. up to about 203° C. and a pressure of in the range of fromabout 30 mm Hg to about 60 mm Hg thereby forming a distillate
 12. Theprocess of claim 5 comprising the additional step of admixing theresulting distillate with a food-approved diluent.
 13. The process ofclaim 5 wherein the said alkadienamides are recovered from thedistillate.
 14. The product produced according to the process of claim5.
 15. The product produced according to the process of claim
 7. 16. Theproduct produced according to the process of claim
 8. 17. The productproduced according to the process of claim
 9. 18. The product producedaccording to the process of claim 10
 19. The product produced accordingto the process of claim
 11. 20. A process for augmenting, enhancing orimparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 1. 21. A process for augmenting, enhancing orimparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 3. 22. A process for augmenting, enhancing orimparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 14. 23. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 15. 24. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 16. 25. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 17. 26. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 18. 27. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material and/or the oral cavity and/or thehuman epidermis comprising the step of admixing with said consumablematerial and/or introducing into the oral cavity and/or applying to saidhuman epidermis an aroma, taste, chemesthetic effect and/orantibacterial effect-effecting concentration and quantity of the productdefined according to claim
 19. 28. The product of claim 5 having themass spectrum-GC profile portion of FIG. 1 or
 2. 29. The composition ofclaim 1 which is synthetically produced and substantially pure.
 30. Aprocess for producing at least one component of the composition of claim3 containing compounds defined according to the structure:

wherein R represents C₁-C₃ n-alkyl; R₁ is 2-methyl-1-propyl and R₂ ishydrogen, or R₁ and R₂ taken together is a moiety having the formula—(CH₂)_(n)— wherein n is 4 or 5 comprising the steps of dissolving anE2, E4-dienoic acid selected from the group consisting of E2,E4-decadienoic acid and E2,E4-undecadienoic acid in a compatible solventthereby forming a E2,E4-dienoic acid solution; admixing the resultingE2,E4-dienoic acid solution with from about 1 to about 2 equivalents ofan acid-activating reagent selected from the group consisting of a loweralkyl haloformate, an N,N′-dialiphatic or cycloaliphaticazodicarbodiimide and a dihalo-oxalate at a temperature in the range offrom about 0° C. to about 20° C. thereby forming an intermediate;cooling the resulting intermediate-containing solution to a temperaturein the range of from about −10° C. to about +10° C. and, when using as areactant the lower alkyl haloformate or the dihalooxalate, admixingtherewith a tri-loweralkyl amine while maintaining the temperature ofthe mixture below +10° C.; then aging the resultingintermediate-containing product at ambient conditions for a period offrom about 0.5 up to about 3 hours; filtering the resulting product;separating the resulting filtrate and cooling the resulting filtrate toa temperature in the range of from about −5° C. to +5° C.; admixing theresulting cooled filtrate with from about 1 to about 4 equivalents of anamine selected from the group consisting of isobutyl amine, piperidineand pyrrolidine at ambient conditions thereby effecting an amidationreaction, and thereby forming an amide defined according to thestructure:

and recovering the resulting amide.
 31. The process of claim 30 whereinan amide is formed having a structure selected from the group consistingof:


32. A process for producing at least one component of the composition ofclaim 3 comprising the steps of: i. carrying out the reaction:

ii. recovering the resulting reaction product.
 33. The product of claim14 in admixture with a composition comprising a sensate selected fromthe group consisting of at least one cooling sensate, at least onewarming sensate, and at least one tingling sensate.
 34. The compositionof claim 33 comprising a substantial quantity and concentration of atingling sensate selected from the group consisting of substantiallypure spilanthol having the structure:

Acmella ciliata, Acmella (Spilanthes) oppositifolia, Anacyclus pyrethrumD.C., Spilanthes acmella L. var. oleraceae (Jambu) and Heliopsislongipes S. F. Blake (Chilcuan).
 35. The composition of claim 34 whereinthe tingling sensate is Acmella ciliata.
 36. A process for augmenting,enhancing or imparting an aroma, taste, chemesthetic effect and/orantibacterial effect in or to a consumable material and/or the oralcavity and/or the human epidermis comprising the step of admixing withsaid consumable material and/or introducing into the oral cavity and/orapplying to said human epidermis an aroma, taste, chemesthetic effectand/or antibacterial effect-effecting concentration and quantity of theproduct defined according to claim
 33. 37. A process for augmenting,enhancing or imparting an aroma, taste, chemesthetic effect and/orantibacterial effect in or to a consumable material and/or the oralcavity and/or the human epidermis comprising the step of admixing withsaid consumable material and/or introducing into the oral cavity and/orapplying to said human epidermis an aroma, taste, chemesthetic effectand/or antibacterial effect-effecting concentration and quantity of theproduct defined according to claim
 34. 38. The composition of claim 1 inadmixture with a composition comprising a sensate selected from thegroup consisting of at least one cooling sensate, at least one warmingsensate, and at least one tingling sensate.
 39. The composition of claim38 comprising a substantial quantity and concentration of a tinglingsensate selected from the group consisting of substantially purespilanthol having the structure:

Acmella ciliata, Acmella (Spilanthes) oppositifolia, Anacyclus pyrethrumD.C., Spilanthes acmella L. var. oleraceae (Jambu) and Heliopsislongipes S. F. Blake (Chilcuan).
 40. The composition of claim 3 inadmixture with a composition comprising a sensate selected from thegroup consisting of at least one cooling sensate, at least one warmingsensate, and at least one tingling sensate.
 41. The composition of claim40 comprising a substantial quantity and concentration of a tinglingsensate selected from the group consisting of substantially purespilanthol having the structure:

Acmella ciliata, Acmella (Spilanthes) oppositifolia, Anacyclus pyrethrumD.C., Spilanthes acmella L. var. oleraceae (Jambu) and Heliopsislongipes S. F. Blake (Chilcuan).
 42. A process for augmenting, enhancingor imparting an aroma, taste, chemesthetic effect and/or antibacterialeffect in or to a consumable material comprising the step of admixingwith said consumable material an aroma, taste, chemesthetic effectand/or antibacterial effect-effecting concentration and quantity of theproduct defined according to claim
 40. 43. A process for augmenting,enhancing or imparting an aroma, taste, chemesthetic effect and/orantibacterial effect in or to a consumable material comprising the stepof admixing with said consumable material an aroma, taste, chemestheticeffect and/or antibacterial effect-effecting concentration and quantityof the product defined according to claim
 41. 44. A process forproduction of a natural amide of claim 3 defined according to astructure selected from the group consisting of:

comprising the steps of: i. forming a natural amine selected from thegroup consisting of isobutyl amine, piperidine and pyrrolidine; ii.forming a natural amine acid salt thereof; iii. optionally neutralizingthe resulting amine salt to form the corresponding amine; iv. providinga natural E2,E4-dienal selected from the group consisting ofE2,E4-decadienal and E2,E4-undecadienal; c. air oxidizing ormicrobiologically oxidizing the resulting E2,E4-dienal thereby formingthe corresponding E2,E4-dienoic acid; vi. esterifying the resultingE2,E4-dienoic acid with natural alkanol or natural glycerol therebyforming the corresponding E2,E4-dienoic acid ester; vii. reacting theresulting E2,E4-dienoic acid ester with the natural amine salt formed instep ii or the natural amine formed in step iii in the presence of anester-forming enzyme; viii. recovering the resulting amide.
 45. Theprocess of claim 44 wherein the ester forming enzyme used in step vii.is lipase.
 46. The process of claim 44 wherein the amine formed isisobutyl amine produced by reacting natural valine with a naturalaromatic ketone or aromatic aldehyde to form an imine carboxylic acid;isomerizing and decarboxylating the resulting imine carboxylic acid toform a decarboxylated imine; hydrolyzing the resulting decarboxylatedimine at a pH of from about 1.5 to about 3.5 thereby forming the naturalisobutyl amine salt.
 47. The process of claim 44 wherein theesterification in step vi. of the E2,E4-dienoic acid is carried out withethanol.
 48. The process of claim 46 wherein the esterification step vi.of the E2,E4-dienoic acid is carried out with natural ethanol.
 49. Aprocess for the production of natural N-isobutyl-E2, E4-decadienamidehaving the structure:

comprising the steps of: i. forming natural isobutyl amine acid salt by(a) reacting natural valine with natural anisaldehyde to form an imine;(b) isomerizing the imine and effecting decarboxylation thereof therebyforming a decarboxylated imine; and (c) effecting acid hydrolysis of thedecarboxylated imine thereby forming the acid salt of isobutyl amine;(d) optionally neutralizing the acid salt of isobutyl amine to formisobutyl amine; ii. forming natural ethyl 2E,4E-decadienoate by (a)thermal isomerization of natural ethyl 2Z,4E-decadienoate; (b)airoxidation of natural 2E,4E-decadienal in admixture with ethanol; or (c)microbiological oxidation of natural 2E,4E-decadienal; iii. reacting theresulting ethyl 2E,4E-decadienoate with the natural isobutyl amine orsalt thereof in the presence of an esterification enzyme with the moleratio of decadienoate:amine or salt thereof being from 1:1 to about 3:1at a temperature of from about 30° C. up to about 80° C. for a period oftime of from about 20 to about 100 hours; and iv. recovering theresulting natural N-isobutyl-E2, E4-decadienamide.
 50. A process foraugmenting, enhancing or imparting an aroma, taste, chemesthetic effectand/or antibacterial effect in or to a consumable material comprisingthe step of admixing with said consumable material an aroma, taste,chemesthetic effect and/or antibacterial effect-effecting concentrationand quantity of a naturally-produced product produced according to claim49.